IC-NRLF 


EXCHANGE 


The  Solubility  of  Liquids  in  Liquids*     The 

Partition  of  the  Lower  Acids  between 

Water  and  Cottonseed  OiL     Also 

the  Partition  of  Formic  Acid 

between  Water  and  Various 

Organic  Compounds 


A  DISSERTATION 


SUBMITTED  TO  THE  BOARD  OF  UNIVERSITY  ^ 

THE  JOHNS  HOPKINS  UNIVERSITY  IN  PARTIAL  ETO- 
FILLMENT  OF  THE  REQUIREMENTS  FOR  THE^  34 
DEGREE  OF  DOCTOR  OF  PHILOSOPHY 


BY  PV 

NEIL  E.  GORDON 

Baltimore,  Maryland 

June,  1917 


EASTON,  PA.: 
ESCHENBACH  PRINTING  Co. 

1922 


The  Solubility  of  Liquids  in  Liquids.     The 

Partition  of  the  Lower  Acids  between 

Water  and  Cottonseed  Oil*     Also 

the  Partition  of  Formic  Acid 

between  Water  and  Various 

Organic  Compounds 


A  DISSERTATION 


SUBMITTED   TO  THE  BOARD  OF  UNIVERSITY  STUDIES  OF 
THE  JOHNS  HOPKINS  UNIVERSITY  IN  PARTIAL  FUL- 
FILLMENT OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF  DOCTOR  OF  PHILOSOPHY 


toMtA] 


BY 

NEIL  E.  GORDON 

Baltimore,  Maryland 
June,  1917 


EASTON,  PA.: 
ESCHENBACH  PRINTING  Co. 


1922 


CONTENTS 

Page 

Acknowledgment 3 

Introduction 5 

Material 11 

Results 11 

Procedure ' 13 

Tables 13-31 

Discussion  of  Results '. 32 

Graphs 35 

Summary ' 41 

Biography 43 


543933 


ACKNOWLEDGMENT 

This  investigation,  having  been  carried  out  under  the 
advice  and  kind  assistance  of  Doctor  Reid,  I  take  this  oppor- 
tunity to  express  my  deep  appreciation  for  the  help  he  has 
given  me.  I  also  feel  under  obligation  to  Drs.  Frazer,  Remsen, 
Lovelace,  and  Gilpin,  for  instruction  and  encouragement 
received.  I  shall  long  remember  the  enthusiastic  personality 
of  the  late  Doctor  Jones,  who  inspired  me  to  take  up  graduate 
work  at  the  Johns  Hopkins  University. 


THE  SOLUBILITY  OF  LIQUIDS  IN  LIQUIDS.  THE 
PARTITION  OF  THE  LOWER  ACIDS,  PARTICULARLY 
FORMIC,  BETWEEN  WATER  AND  VARIOUS  ORGANIC 

SOLVENTS1 


That  some  substances  dissolve  when  brought  into  contact 
with  various  liquids  must  have  been  one  of  the  first  observations 
that  can  be  classed  as  chemical.  In  the  last  three  decades  the 
study  of  solutions  has  been  the  chief  occupation  of  chemists. 
Yet  our  knowledge  of  solutions  is  still  far  from  adequate  and 
some  of  our  conceptions  are  still  not  clear. 

If  we  shake  a  portion  of  water  with  oxygen,  another  por- 
tion with  ether,  and  a  third  with  sugar,  assuming  constant 
temperature,  equilibria  are  reached  and  we  call  the  three  solu- 
tions saturated,  speaking  of  the  concentrations  of  the  three 
solutes  in  the  water  as  their  solubilities.  The  words  "saturated 
and  solubility"  are  used  for  all,  but  actually  have  quite  differ- 
ent meanings  in  the  three  cases. 

The  solubility  of  the  sugar  is  definite,  since  in  that  case 
the  solid  phase  is  pure  sugar,  unchanged  in  composition  and 
concentration  by  its  contact  with  the  water.  In  the  case  of 
the  oxygen  and  water,  the  only  thing  that  we  can  determine 
is  the  ratio  of  the  concentrations  of  oxygen  in  the  two  phases. 
Since  the  water  vapor  does  not  affect  the  partial  pressure  of 
the  oxygen,  this  ratio  is  definite  and  independent  of  the  water 
vapor  present  in  the  gas  phase.  As  previously  pointed  out2 
while  the  solubility  of  the  ether  is  definite,  yet  the  solubility 
that  we  find  is  not  the  true  solubility,  i.  e.,  the  amount  of  ether 
taken  up  by  water  in  contact  with  anhydrous  ether.  We  can 
no  more  determine  the  solubility  of  ether  in  water  than  we  can 


1  Contribution  from  the  Chemical  Laboratory  of  the  Johns  Hopkins 
University. 

2  Wroth  and  Reid:  Jour.  Am.  Chem.  Soc.,  38,  2316  (1916). 


6 

that  of  formic  acid,  since  we  cannot  have  a  solution  of  either 
ether  or  formic  acid  in  contact  with  the  anhydrous  liquid. 
We  may  hope  that  sometime  a  method,  or  formula,  may  be 
devised  for  finding  the  true,  or  ideal,  solubility  of  ether  in 
water,  perhaps  from  the  observed  equilibrium  of  the  solution 
of  ether  in  water  with  one  of  water  in  ether,  perhaps  from 
some  other  data. 

In  the  case  of  solid  iodine,  where  the  solubilities  are  true 
solubilities,  Jakowkin1  found  the  ratio  of  the  solubilities  in  two 
solvents,  Sa/Sb,  remarkably  near  to  the  partition  ratio,  Ca/Cb, 
or  r,  measured  with  the  same  two  solvents.  He  further  found 
that  r  changes  progressively,  approaching  more  and  more 
nearly  the  value  Sa/Sb  as  the  concentrations  of  iodine  in  the 
two  solvents  increase,  i.  e.,  as  Ca/Cb  approaches  Sa/Sb  as  Ca 
and  Cb  aproach  Sa  and  Sb. 

As  is  well  known,  the  partition  ratio,  r,  remains  constant 
with  changing  concentrations,  only  when  the  substance  par- 
titioned dissolves  in  both  solvents  in  the  same  form.  Further- 
more, it  is  stipulated  that  the  two  solvents  must  be  absolutely 
insoluble  in  each  other,  even  when  both  contain  large  amounts 
of  the  common  solute.  This  condition  is,  of  course,  never 
more  than  approximately  fulfilled,  the  disturbing  influences 
becoming  greater,  the  higher  the  concentrations  of  the  solute. 

In  the  present  investigation  formic  acid  has  been  parti- 
tioned between  water  and  the  following  solvents:  cottonseed 
oil,  kerosene,  benzene,  toluene,  xylene,  carbon  tetrachloride, 
carbon  disulphide  and  bromoform.  The  so-called  solubilities 
of  formic  acid  in  these  eight  solvents  and  the  solubilities  of 
these  liquids  in  formic  acid  have  been  determined. 

If  the  solubility  figure  found  for  formic  acid  in  benzene, 
say,  were  the  ideal  solubility  and  the  partition  ratio  found 
were  correct,  then  the  product  of  these  two  should  give  the 
ideal  solubility  of  formic  acid  in  water  which  we  cannot  find 
directly.  The  ideal  solubility  from  the  data  obtained  from 
these  eight  solvents  should  be  the  same,  or,  since  the  several 

*  Zeit.  phys.  Chem.,  18,  590  (1895). 


partition  ratios  vary  with  the  concentrations,  the  values 
found  should  tend  to  approach  some  one  limit,  as  the  concen- 
trations of  formic  acid  in  the  non-aqueous  solvents  approach 
the  solubilities  of  formic  acid  in  these  solvents. 

In  the  case  of  carbon  disulphide  and  water,  and  in  that 
only,  the  partition  ratio  remained  practically  constant  with 
changing  concentration,  being  1606  when  the  acid  in  the  water 
layer  was  8.4%  and  1616  when  this  had  increased  to  54.8%. 
When  carbon  disulphide  and  formic  acid  are  shaken  together 
there  is  1.28  g  of  the  acid  to  100  g  carbon  disulphide  in  the 
one  layer  and  4.66  g  carbon  disulphide  to  100  g  formic  acid 
in  the  other.  Even  in  this  case  1.28  is  not  the  ideal  solu- 
bility of  formic  acid  since  the  solution  was  in  contact  with  a 
mixture  of  95.55%  formic  acid- and  4.45%  carbon  disulphide 
and  not  with  the  pure  acid,  but  as  in  this  case  the  mutual 
"solubilities"  are  the  lowest  and  the  partition  ratio  is  the  most 
nearly  constant,  this  appears  to  be,  by  far,  the  most  favorable 
case.  Multiplying  1.28,  the  "solubility"  of  formic  acid  in 
carbon  disulphide,  by  the  partition  ratio,  1616,  we  have  2068 
as  the  ideal  solubility  of  formic  acid  in  water,  i.  e.,  2068  g  of 
the  acid  should  be  taken  up  by  100  g  of  water  in  contact  with 
anhydrous  formic  acid,  a  condition  which  can,  of  course,  never 
be  realized.  With  the  other  seven  solvents  the  products  of 
the  several  solubilities  by  the  respective  partition  ratios 
should  approach  2068  as  the  concentrations  increase.  That 
is  the  figures  in  the  last  columns  of  Tables  1  and  7-12  should 
approach  2068  as  we  read  down.  The  results  are  represented 
graphically  in  Fig.  1  in  which  these  hypothetical  ideal  solu- 
bilities are  plotted  against  the  percentage  of  saturation  of  the 
non-aqueous  layer.  The  curves  as  drawn  extend  only  to  8%, 
not  far  enough  to  include  all  the  points  on  the  kerosene, 
cottonseed  oil  and  bromoform  curves.  For  very  dilute  solu- 
tions the  figures  obtained  are  more  or  less  erratic  on  account 
of  the  difficulties  involved  in  determining  the  small  amounts 
of  acid  present  in  even  large  amounts  of  the  oil  layers,  e.  g.,  in 
the  most  dilute  solution  with  carbon  tetrachloride  the  amount 
of  formic  acid  per  100  g  of  oil  was  only  0.0038  g. 


8 


Most  of  the  series  were  terminated  at  55%  to  60%  of 
formic  acid  in  the  water  layer  as  it  was  thought  that  results 
with  greater  concentrations  could  not  be  trusted  on  account 
of  mutual  solubilities  of  the  two  solvents  in  presence  of  so 
much  of  the  solute.  But  with  cottonseed  oil  the  concentra- 
tion was  carried  up  to  87.2%  of  formic  acid  in  the  water  layer 
when  there  was  5.026  g  of  acid  per  100  g  of  the  oil  layer  while 
the  solubility  of  the  anhydrous  acid  in  the  oil  is  8.68  g  per 
100  g.  This  gives  us  a  point  in  the  cottonseed  oil  curve  at  58% 
for  which  the  ordinate  is  1179  which  is  well  on  the  way  to  the 
figure  indicated  by  the  carbon  disulphide  curve. 


PERCENT  OF  POSS/k. 


'LE 


Fig.  1 


JD  IN  THE  OIL. 


It  is  interesting  to  note  that  cottonseed  oil  takes  up  only 
58%  as  much  formic  acid  from  an  87%  acid  as  from  the  100% 
acid.  On  a  molecular  basis  73%  of  the  molecules  are  formic 
acid,  so  it  appears  that  the  water  in  the  acid  is  more  than  a 
diluent:  it  restrains  the  formic  acid  molecules  from  passing 
into  the  oil  layer.  A  similar  inference  may  be  drawn  from 
other  experiments.  In  most  cases  where  the  water  layer  con- 


9 


tains  over  50%  of  formic  acid  the  oil  layer  takes  up  only  5%  to 
7%  as  much  acid  as  from  100%  formic  acid. 

The  results  with  kerosene  are  regarded  as  unreliable  as 
the  oil  layer  was  much  colored  at  the  higher  concentrations 
indicating  some  sort  of  reaction. 

Looking  at  the  figure,  there  appears  to  be  a  tendency  for 
the  various  curves  to  converge  on  the  carbon  disulphide  line 
indicating  an  ideal  solubility  around  2000,  though  the  bromo- 
form  curve  is  very  low  down  and  the  one  for  cottonseed  oil  has 
a  considerable  distance  to  go.  The  xylene  curve  appears  to 
cross  the  2000  line.  It  is  certainly  hazardous  to  extrapolate 
from  6  or  8%  to  100%. 


/  CAR  RON  TETRACHLORjnE 

2  BENZENE 

3  TOLUENE 
4-  XYLENE 

5  CARBON  D1SULPH/DE 

6  KEROSENE 


Z  5  4 

OF  POSSIBLE    FORMIC 


Fig.  2 


0/L 


In  Fig.  2  the  same  data  are  presented  on  a  different  basis; 
the  ordinates  are  the  same  but  the  abscissae  are  the  percentage 
of  formic  acid  in  water  layer  at  equilibrium.  On  this  basis 
the  curves  are  steeper  and  do  not  show  as  much  tendency  to 
converge  though  we  have  the  advantage  of  having  to  extra- 
polate over  a  much  shorter  distance,  as  all  of  the  curves  go 
as  far  as  55%  and  one  even  to  87%. 


10 


The  results  obtained  do  not  settle  the  question  but  it  is 
hoped  they  do  open  it.  One  method  of  approach  has  been 
tried :  better  ones  may  be  found.  Even  by  this  method  more 
measurements  are  desirable  at  higher  concentrations,  with 
other  solvents,  and  with  other  solutes.  The  results  so  far 
obtained  have  value  as  partition  and  solubility  measurements. 
The  degrees  of  association  of  formic  acid  in  the  various  solvents 
can  be  calculated  from  the  variation  of  the  partition  ratios. 


120 


WO 


1 


60 


PTiOPJONIC 


-/BUTYRIC 


t 


PERCENT  OF  ACID  IN  WATER  LAYER 
Fig.  3 

As  formic  acid  is  a  strong  acid,  its  dissociation  in  the  water 
layer  influences  the  partition  ratios,  but  as  its  lowest  concen- 
tration was  0.24  N,  at  which  it  is  only  moderately  dissociated 
and,  as  it  turned  out,  the  high  concentrations  are  the  ones 
which  are  of  most  interest  from  the  present  point  of  view,  the 
dissociation  may  be  disregarded.  It  is  interesting  to  note 
that  formic  acid  shows  a  real  partition  ratio  in  all  cases  even 
in  dilute  solution,  which  is  in  marked  contrast  to  the  behavior 
of  silver  perchlorate  as  found  by  Hill.1 

1  Jour.  Am.  Chem.  Soc.,  43,  254  (1921). 


11 

Georgievics1  partitioned  formic  acid  between  benzene 
and  water.  Calculating  his  results  according  to  our  method 
we  obtain  the  following  partition  ratios : 

%Acid    4.4     5.8     6.7     7.8    8.6     8.7     13.3     13.3     18.9     23.9 
Ratio       370     261     400     302     264     562      304      347      269      298 

Disregarding  the  sixth,  the  average  of  these  is  316  which  is 
not  far  from  292  the  average  of  our  results  over  the  same  range. 
In  addition  to  the  experiments  with  formic  acid,  acetic, 
propionic  and  butyric  were  partitioned  between  cottonseed  oil 
and  water  and  acetic  acid  between  kerosene  and  water.  The 
partition  ratios  are  plotted  in  Fig.  3.  The  proportion  of  the 
organic  acid  taken  by  the  water  layer  increases  rapidly  as  we 
go  from  formic  to  butyric.  The  formic  acid  curve  bends 
sharply  upward  at  about  70%  of  acid  in  the  water  layer.  Acetic 
acid  has  a  definite  solubility  in  the  oil  but  propionic  and  butyric 
have  not.  Formic  is  the  only  one  of  these  that  shows  limited 
solubility  in  the  other  solvents. 

Materials 

Cottonseed  Oil:  The  Wesson  oil  used  was  found  to  have 
an  acid  reaction.  In  order  to  eliminate  this  the  oil  was  shaken 
with  a  dilute  solution  of  barium  hydroxide  for  an  hour.  It 
was  then  centrifuged  and  filtered,  when  it  gave  a  perfectly 
neutral  reaction. 

Formic  Acid:  This  was  distilled  under  reduced  pressure 
over  anhydrous  copper  sulphate  as  suggested  by  Garner, 
Saxton  and  Parker.  The  pressure  used  was  120  mm,  when 
the  acid  distilled  over  at  50°.  This  method  was  found  to  be  a 
very  satisfactory  one.  Beginning  with  an  acid  89.2  percent 
pure,  the  first  distillation  resulted  in  an  acid  96.5  percent,  the 
second  98.2  percent,  and  the  third  distillation  gave  an  acid 
99.99  percent  pure.  This  acid  melted  at  8.35 °  and  had  density 
1.2170|.2  This  anhydrous  acid  was  used  for  the  solubility 
work  only.  For  the  partition  work,  commercial  acid  was  used 

1  Zeit.  phys.  Chem.,  84,  359  (1913). 

2  Am.  Chem.  Jour.,  46,  236  (1911);  J.,  1886,  216. 


12 

since  it  was  found  to  contain  only  water.  The  water  it  con- 
tained was  calculated  and  added  to  the  weight  of  wate,r 
taken. 

Acetic  Acid:  Like  formic  acid  the  commercial  acid  was 
used  for  the  partition  work.  For  the  solubility  the  acid  was 
purified  by  freezing.  It  was  found  that  the  number  of  freez- 
ings necessary  to  render  it  anhydrous  could  be  cut  down  by 
introducing  a  crystal  of  the  acid  to  prevent  too  great  undercool- 
ing. It  melted  at  16.7°,  and  titrated  99.9  percent  pure.  Its 
density  was  1.0445||. 

Propionic  and  Butyric  Acids:  These  acids  mixed  in  all 
proportions  with  both  oil  and  water  and  thus  it  was  not  nec- 
essary to  make  them  anhydrous.  As  their  densities  and 
titrations  showed  they  contained  only  water  as  an  impurity, 
they  were  used  without  further  purification. 

Organic  Solvents:  First  class  commercial  grades  of  ben- 
zene, toluene,  xylene,  carbon  tetrachloride,  carbon  disulphide, 
and  bromoform  were  used.  To  insure  purity,  the  boiling  points 
and  densities  were  taken  and  found  to  agree  well  with  those 
given  in  the  literature. 

Waddell1  found  in  his  investigation  that  the  same  partition 
coefficient  was  given  with  purified  benzene  as  with  commercial 
benzene. 

Standard  Solutions:  Standard  solutions  of  approximately 
N/10  were  prepared,  and  frequently  standardized.  The  solu- 
tions were  kept  in  large  stock  bottles  from  which  they 
were  siphoned  into  the  burettes.  The  barium  hydroxide 
bottle  and  burettes  were  protected  from  the  air  by  tubes  con- 
taining soda  lime. 

Water:     Freshly  distilled  water  was  used. 

Kerosene  Oil:  Commercial  kerosene  oil  was  distilled 
and  the  portion  obtained  between  180°  and  260°  was  used 
in  the  partition  work.  It  had  a  density  of  0.798ff. 

1  Jour.  Phys.  Chem.,  2,  233  (1895). 


13 

Procedure 

The  filling,  shaking  and  centrifuging  of  the  bottles  con- 
taining cottonseed  oil,  water  and  the  respective  acids  was 
carried  out  approximately  as  the  former  work  where  the  alco- 
hols were  used  instead  of  the  acids.  It  seemed  necessary  to 
shake  the  acids  longer  than  the  alcohols  to  obtain  concordant 
results.  The  centrifuge  was  used  only  with  the  cottonseed 
oil  and  water. 

Estimation  of  Acids  in  Non-aqueous  Solvent  Layers. — The 
oil  layer  containing  the  acid  was  drawn  off  by  means  of  a  spe- 
cial pipet,  shaped  similar  to  the  Ostwald  pycnometer.  An 
amount  of  oil  was  taken  out  with  the  pipet  sufficient  to  re- 
quire about  10  cc  of  the  barium  hydroxide  for  neutralization. 
The  oil  was  put  into  a  180-cc  beaker  containing  about  80  cc  of 
distilled  water  for  titration.  The  oil,  with  ordinary  stirring 
failed  to  give  up  its  acid  promptly,  making  the  titration  slow 
and  uncertain.  A  mechanical  stirrer  was  used  and  this  ac- 
celerated the  speed  with  which  the  acid  passed  from  the  oil 
into  the  water.  Even  under  these  conditions  the  end-point  was 
not  as  accurate  as  it  was  in  the  water.  In  spite  of  all  efforts 
the  acid  seemed  to  have  a  slight  tendency  to  cling  to  the  oil. 
The  other  organic  solvents  were  handled  similarly. 

Estimation  of  Acid  in  Water  Layer. — A  small  thin-walled 
glass  bulb  was  weighed,  partly  filled  from  the  water  layer, 
sealed  and  reweighed.  The  bulb  was  then  broken  under  water 
to  avoid  evaporation,  and  the  amount  of  acid,  which  it  con- 
tained was  determined  by  titration. 

The  absolute  solubilities  of  formic  and  acetic  acids  in 
cottonseed  oil  were  found  by  shaking  the  oil  and  anhydrous 
acids  in  the  constant  temperature  bath  for  four  hours,  and  then 
estimating  the  amount  of  acid  in  the  oil  layer  and  the  amount 
of  oil  in  the  acid  layer  by  the  titration  method  as  just  de- 
scribed. The  absolute  solubility  of  formic  acid  in  the  other 
organic  solvents  used  and  the  solubility  of  the  solvents  in  the 
formic  acid  were  carried  out  in  a  similar  manner. 


14 


Solubilities  at  25 


Formic  Acid  in  Cottonseed  Oil 

Cottonseed  Oil  in  Formic  Acid 

Sample 

Found 

In  100  g 

Sample 

Found 

In  100  g 

0.3154 
0.1656 
0.4437 
0.5019 

0.0251 
0.0416 
0.0360 
0.0393 

8.65 
8.72 
8.84 
8.50 

0.1656 
0.1141 
0.1086 
0.1142 

0.0013 
0.0009 
0.0008 
0.0009 

0.78 
0.79 
0.74 
0.79 

Av.  8.68 


Av.  0.77 


Acetic  Acid  in  Cottonseed  Oil 

Cottonseed  Oil  in  Acetic  Acid 

0.1421 
0.0858 
0.0831 
0.0684 
0.1008 

0.0508 
0.0309 
0.0299 
0.0245 
0.0345 

55.4 
56.3 
56.3 
55.96 
54.3 

0.1016 
0.0996 
0.0616 
0.1373 
0.0894 

0.0058 
0.0055 
0.0036 
0.0073 
0.0050 

5.8 
5.5 
5.7 
5.6 
5.6 

Av.  55.7 


Av.  5.6 


Formic  Acid  in  Benzene 


Benzene  in  Formic  Acid 


Sample 

Found 

In  100  g 

Sample 

Found 

In  100  g 

0.2718 
0.3300 
0.3950 
0.4277 
0.4197 

0.0341 
0.0416 
0.0502 
0.0537 
0.0527 

14.3 
14.4   ' 
14.5 
14.3 
14.40 

0.1825 
0.0992 
0.1455 
0.0030 

0.0238 
0.01312 
0.0189 
0.0122 

15.0 
15.2 
14.9 
15.4 

Av.  14.40 


Av.   15.14 


Formic  Acid  in  Toluene 

Toluene  in  Formic  Acid 

0.2815 
0.3795 
0.2986 
0.3565 

0.0284 
0.0376 
0.0295 
0.0358 

11.20 
10.98 
10.96 
11.17 

0.1793 
0.1323 
0.0851 

0.0149 
0.0110 
0.0071 

9.08 
9.06 
9.10 

Av.  11.08                                              Av.  9.08 

Formic  Acid  in  Xylene 

Xylene  in  Formic  Acid 

0.5440 
0.3535 
0.4480 

0.0442 
0.0251 
0.0357 
1 

8.83 
8.70 
8.70 

0.1009 
0.0790 

0.0063 
0.0057 

^ 

6.81 

7.77 

Lv.  7~29 

^v.  8.74 

15 


Solubilities  at  25 


Formic  Acid  in  Carbon 
Tetrachloride 

Carbon  Tetrachloride  in 
Formic  Acid 

0.1910 
0.3434 
0.3623 
0.3158 

0.0069 
0.0115 
0.0119 
0.0105 

(3.76) 
3.45 
3.40 
3.44 

0.0484 
0.0934 
0.0918 

0.0030 
0.0062 
0.0063 

6.60 
6.95 
7.31 

Av.  3.43 


Av.  6.95 


Formic  Acid  in  Carbon 
Bisulphide 

Carbon  Bisulphide  in  Formic 
Acid 

2.4628 
1.9878 
2.6070 
4.7033 
4.9431 
7.461 

0.0313 
0.0240 
0.0311 
0.0549 
0.0569 
0.0959 

1.29 

1.28 
(1.21) 
(1.18) 
(1.16) 
1.29 

0.0631 
0.1429 

0.0604 
0.1398 

4.47 
4.85 

Av.  1.28 


Av.  4.66 


Formic  Acid  in  Bromoform 

Bromoform  in  Formic  Acid 

1.9684 
1.2830 
3.2351 

0.0475 
0.0310 
0.0767 

2.47 
2.47 
2.42 

0.1301 
0.1085 

0.0362 
0.0220 

25.2 
25.4 

Av.  2.45 


Av.  25.3 


Formic  Acid  in  Kerosene 

Kerosene  in  Formic  Acid 

Sample 

Found 

In  100  g 

Sample 

Found 

In  100  g 

3.3003 
2.9977 

0.0294 
0.0267 

0.899 
0.905 

0.1003 
0.0681 

0.0015 
0.0011 

1.52 
1.60 

0.897 


1.56 


Acetic  Acid  in  Kerosene 


Kerosene  in  Acetic  Acid 


1.0690 
0.7638 

0.1909 
0.1367 

21.74 
21.80 

0.0735 
0.0802 

0.0082 
0.0088 

12.6 
12.3 

Av.  21.77 


Av.  12.4 


16 


Partition  Experiments 

The  results  are  given  in  the  tables  below,  no  completed 
determination  being  omitted,  the  first  column  showing  the  final 
percentage  of  acid  in  the  water  layer,  the  next  three  the  amounts 
of  water,  oil  and  acid  weighed  in,  while  the  fifth  and  sixth  give 
the  amounts  of  acid  found  in  the  two  layers,  the  sum  of  these 
should  equal  the  weight  of  acid  in  column  four.  In  the  sev- 
enth is  found  the  molecular  partition  ratio  or  the  acid  dissolved 
by  1  mol.  of  water  divided  by  that  dissolved  by  1  mol.  of  the  oil. 
The  m.  wt.  of  cottonseed  oil  was  assumed  to  be  885.  In  the 
case  of  kerosene  this  ratio  is  omitted.  The  next  column  gives 
the  partition  ratio  for  equal  weights  of  water  and  oil  and  the 
last  gives  this  weight  ratio  multiplied  by  the  solubility  of  the 
acid  in  the  oil  when  this  is  known. 


TABUS  1 
Partition  of  Formic  Acid  between  Cottonseed  Oil  and  Water 


% 

Acid 

Water 

Oil 

Acid 

Weight  acid  in 

Partition  ratios 

Weight 
ratio 
X  8.68 

Water 

Oil 

Molec- 
ular 

Weight 

1.1 

15.42 

66.85 

0.183 

0.169 

0.0115 

1.29 

63.6 

552 

2.3 

16.94 

70.53 

0.423 

0.399 

0.0253 

1.33 

65.7 

570 

3.7 

14.57 

75.37 

0.595 

0.556 

0.0430 

1.36 

66.8 

580 

4.2 

22.54 

72.63 

1.036 

0.990 

0.0471 

1.38 

67.8 

588 

5.5 

22.66 

67.69 

1.385 

1.326 

0.0592 

1.36 

66.9 

581 

8.1 

12.05 

81.52 

1.163 

1.064 

0.1064 

1.38 

67.7 

588 

12.7 

27.00 

63.19 

4.077 

3.945 

0.1224 

1.54 

75.4 

654 

14.4 

6.84 

5.91 

1.166 

1.152 

0.0130 

1.56 

76.5 

664 

20.9 

13.11 

20.47 

3.556 

3.470 

0.0680 

1.62 

79.7 

692 

30.3 

5.57 

6.576 

2.500 

2.429 

0.0323 

1.87 

91.9 

798 

32.4 

12.62 

22.87 

6.168 

6.045 

0.1192 

1.81 

88.8 

771 

51.1 

4.54 

5.051 

4.827 

4.747 

0.0563 

1.91 

93.9 

815 

62.5 

3.65 

5.857 

6.258 

6.087 

0.0997 

1.99 

97.9 

850 

71.3 

3.16 

4.981 

8.043 

7.854 

0.1241 

2.03 

99.5 

864 

80.7 

1.79 

6.102 

7.720 

7.463 

0.2222 

2.34 

114.8 

996 

86.3 

0.799 

7.728 

5.493 

5.023 

0.3705 

2.67 

131.1 

1138 

87.2 

0.72S 

8.589 

5.894 

4.972 

0.4317 

2.76 

135.8 

1179 

17 


TABLE  2 
Partition  of  Acetic  Acid  between  Cottonseed  Oil  and  Water 


% 

Acid 

Water 

Oil 

Acid 

Weight  acid  in 

Partition  ratios 

Weight 
ratio 
X55.7 

Water 

Oil 

Molec- 
ular 

Weight 

1.9 

25.84 

68.32 

0.544 

0.5105 

0.0363 

0.757 

37.2 

2071 

2.1 

24.32 

66.23 

0.550 

0.5130 

0.0364 

0.781 

38.4 

2137 

2.4 

26.70 

65.86 

0.696 

0.6504 

0.0463 

0.705 

34.6 

1930 

7.5 

27.51 

71.33 

2.408 

2.238 

0.1711 

0.690 

33.9 

1888 

8.  '2 

26.31 

64.31 

2.513 

2.346 

0.1718 

0.671 

33.4 

1859 

12.7 

26.68 

68.80 

4.185 

3.877 

0.3006 

0.677 

33.3 

1853 

14.1 

28.28 

69.97 

4.9751 

4.636 

0.3471 

0.672 

33.0 

1840 

16.2 

24.75 

67.27 

5.195 

4.791 

0.3940 

0.673 

33.1 

1841 

28.9 

13.13 

25.64 

5.673 

5.345 

0.3177 

0.667 

32.9 

1830 

31.8 

11.13 

25.35 

5.534 

5.178 

0.3453 

0.695 

34.2 

1903 

46.9 

4.38 

5.950 

4.044 

3.875 

0.1424 

0.752 

36.9 

2059 

50.9 

4.360 

6.064 

4.729 

4.516 

0.1720 

0.743 

36.5 

2035 

62.1 

1.387 

7.574 

2.586 

2.270 

0.3118 

0.809 

39.7 

2212 

70.2 

1.001 

7.572 

2.794 

2.361 

0.4311 

0.843 

41.4 

2308 

81.8 

1.958 

5.975 

9.574 

8.827 

0.6483 

0.845 

41.5 

2314 

Partition  of  Propionic  Acid  between  Cottonseed  Oil  and  Water 


% 

Acid 

Water 

Oil 

Acid 

Weight  acid  in 

Partition  ratios 

Water 

Oil 

Molecular 

Weight 

3.4 
7.4 
14.3 
23.0 
36.2 
59.8 
62.5 
67.3 

38.15 
39.75 
20.05 
15.09 
3.416 
2.988 
0.8750 
0.4755 

48.33 
42.39 
20.09 
20.88 
7.705 
5.516 
7.750 
8.919 

1.620 
3.836 
4.045 
5.855 
2.744 
5.311 
2.853 
2.873 

1.347 
3.165 
3.335 
4.502 
1.938 
4.438 
1.458 
0.979 

0.2819 
0.6580 
0.7240 
1.358 
0.7779 
0.8959 
1.366 
1.874 

0.123 
0.104 
0.094 
0.093 
0.114 
0.186 
0.192 
0.199 

6.05 
5.13 
4.62 
4.59 
5.60 
9.14 
9.45 
9.79 

18 


TABLE  4 
Partition  of  Butvric  Acid  between  Cottonseed  Oil  and  Water 


% 

Acid 

Water 

Oil 

Acid 

Weight  acid  in 

Partition  ratios 

Water 

Oil 

Mblecular 

Weight 

2.7 
5.0 
9.2 
14.0 
30.5 
41.3 

16.135 
16.568 
6.530 
3.139 
3.911 
1.802 

24.590 
25.095 
6.562 
6.755 
6.597 
6.590 

0.747 
1.612 
1.164 
1.308 
3.458 
3.203 

0.4526 
0.8798 
0.6615 
0.5106 
1.714 
1.268 

0.2764 
0.7350 
0.4906 
0.7880 
1.692 
1.948 

0.0508 
0.0369 
0.0276 
0.0284 
0.0348 
0.0484 

2.495 
1.813 
1.355 
1.395 
1.709 
2.380 

TABLE  5 
Partition  of  Formic  Acid  between   Kerosene  and  Water 


%  Acid 

Water 

Oil 

Acid* 

Weight  acid  in 

Partition 
ratio 
Weight 
ratio 

Weight 
ratio 
X  0.897 

Water 

Oil 

17.9 
30.9 
38.9 
43.2 
59.8 
66.3 

10.634 
9.801 
9.778 
2.547 
2.725 
3.153 

65.717 
72.723 
65.189 
7.422 
5.645 
30.950 

2.324 
4.452 
6.283 
1.945 
4.160 
6.400 

2.316 
4.388 
6.224 
1.936 
4.060 
6.200 

0.00648 
0.01586 
0.02146 
0.00308 
0.00714 
0.05358 

2209 
2052 
1933 
1831 
1180 
1136 

1981 
1841 
1734 
1642 
1058 
1019 

TABLE  6 
Partition   of  Acetic  Acid  between   Kerosene   and   Water 


%  Acid 

Water 

Oil 

Acid 

Weight  acid  in 

Partition 
ratio 
Weight 
ratio 

Weight 
ratio 
X  21.77 

Water 

Oil 

9.1 
17.0 
27.2 
46.9 
59.2 

7.110 
6.027 
6.786 
2.503 
2.819 

32.024 
30.676 
29.831 
8.479 
6.243 

0.730 
1.392 
2.665 
2.330 
4.273 

0.7127 
1.236 
2.532 
2.214 
4.089 

0.02164 
0.05796 
0.1332 
0.09804 
0.1217 

1483 
1086 
836 
765 
744 

32300 
23600 
18200 
16700 
16200 

19 


TABLE  7 
Partition   of   Formic   Acid   between   Benzene   and   Water 


% 

Acid 

Water 

Oil 

Acid 

Weight  acid  in 

Partition  ratios 

Weight 
ratio 
X  14.40 

Water 

Oil 

Molec- 
ular 

Weight 

5.3 
6.4 
9.9 
13  .  6 

18.5 
29.2 
41.2 

58.2 

20.61 
11.46 
19.96 
21.71 
28.39 
10.30 
12.71 
3.272 

74.21 
89.07 
82.54 
65.42 
51.66 
28.71 
32.92 
40.73 

1.138 
0.742 
2.195 
3.444 
6.506 
4.395 
9.126 
5.096 

1.146 
0.716 
2.192 
3.432 
6.437 
4.258 
8.894 
4.695 

0.0126 
0.0175 
0.0329 
0.0382 
0.0434 
0.0449 
0.1060 
0.3279 

75.1 
73.5 
63.5 
62.4 
62.3 
61.0 
50.8 
41.1 

327 
319 
275 
270 
270 
264 
220 
178 

4710 
4590 
3960 
3890 
3890 
3810 
3170 
2570 

TABLE  8 
Partition  of  Formic  Acid  between  Toluene  and  Water 


% 

Acid 

Water 

Oil 

Acid 

Weight  acid  in 

Partition  ratios 

Weight 
ratio 
X  11.08 

Water 

Oil 

Molec- 
ular 

Weight 

5.3 

7.9 
16.5 
31.0 
41.7 
59.7 

21.04 
20.43 
10.319 
9.210 
5.618 
3.276 

79.04 
64.20 
88.00 
84.70 
30.87 
32.68 

1.174 
1.799 
2.086 
4.257 
4.181 
5.186 

1.177 
1.761 

2.039 
4.148 
4.019 
4.834 

0.0118 
0.0158 
0.0498 
0.1166 
0.0837 
0.2391 

74.0 
68.5 
68.5 
64.0 
52.8 
39.5 

378 
350 
349 
327 
270 
202 

4190 
3880 
3870 
3620 
2990 
2230 

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